New polyepoxides from epoxy-substi-tuted cycloaliphatic alcohols, their preparation and polymers



':aliphatic ring;

v v Y I 2,92 ,40 V NEW POLYEPOXIDES FROM, 1 EPOXY-SUBSTL 'TUTED CYCLOALIPHATIC ALCOHOIS, .THEIR J rRErARArIo ANDPOLYMERS.

Edward .C. Shokal,' Walnut Creek, Calif iassignor l Shell Development Company, New York, N.Y., aeor- 7 poration of Delaware I v I h 7 H No Drawing. AppIicationMayZD, 1956 1 sm mmsswso- I 18 Claims. '(Cl,260147) 'Thisinvention relates to a new class of .polyepoxides and to a method for their preparation. ,More particu-. larly, the invention relates to new polyepoxides derived from epoxy-substituted cycloaliphatic alcohols, to a meth od for their preparation and to the utilization of the new polyepoxides, particularly in the preparation of pot- 10 V t g It has'been' further found, and this represents a special Pa ent d eb- ,1 6

types of polyepoxidesysuch as .thecomme'rciallyiavailw ble'glycidyl ethers. of polyhydric phenols it has also been round that t'hese' new polyepoxldes' having high ac tiv tytoward; epoxy' cur n g'agent's, suchfas amines,.an-

hydrides', Br; andiBF eomp1exes, can be' used therewith to form very hard resistantjproducts; This was quite unexpected as previou sty prepared polyepoxideshaving the epoxy group 'inan'internal pos tion, such as, for

example',epoxiorz'ed triglycerides, have been very slow to fr'eact with epoxy cur ng'agents, such as amines.

feature of the inventiomthat'the 'new' polyepoxides prepared from the ep xy Substituted cycloauphatic alcohols tings and castings and in the preparation of improved coating compositions. I

Specifically, the invention provides new and particularly useful polyepoxides comprising ethers of (1) alcohols having a Vic-epoxy group contained in a c ycloali;

phatic ring, and (2){monohydric alcohols 'possessingone or more vie-epoxy. groups. These. new polyepoxides are, 7

preferably preparedby etherifying analcohol having 'an ethylenically unsaturated cyeloaliphatic*'r ing,suchias, fo

example, 2-cyclohexenol, ,with'fa' vic-epoxy-substituted V Theinvention further provides cured 'productsflobtained by reacting the above-described'new polyepoxides with. epoxy'curing agents, such as amines, polybasicacid anhydrides, BF, and its complexes, metal salt catalysts and the like. 1

his an object of the invention to provide'a newj class alcoho'lgsuch as, for examplefglycido'l', and then treat ing the resulting ether with a peroxidizing agent to convert the ethylenic group in-the cyclo'aliphaticring to of polyepoxides and a method for their preparation. It

"is a further object to providenew polyepoxides from alcohols possessing an ethylenically unsaturated cyclo :aliphatic polyepoxideswhich possesslowvi s'cosities. -It

' is a further, object to provide new non-.aromaticpolyepoxides which have a high, degree of reactivity with epoxy curingagents, suchflasamines and anhydridesi It It is a further object to provide new.

; compounds has isstill a further object to provide new non-aromaticpoly epoxides which have epoxy'groups having difierentrates 'of reactivity with epoxy curing agents." his a further object to provide new non-aromatic polyepoxide's which I can react with a curing agent through one epoxy group an then cross-linked with a diiferentTcuring'a'g'ent through the remaining epoxy groups, ,It is, a. further object to provide new non-aromatic polyepoxideswlhich can from th'e followingdetailed description; thereof.- 1 f i It has now been discovere'd that these'and other ob'- be cured tofor m hard resistant castings, Other ob jects and' advantages,of-the invention willtbe apparent jects may be accomplished byithe new polyepoxidestof the present invention which comprise ethers of (1 alcohols having avic-epoxy group contained in a c'yclo- V alcohols possessing one or expression fvid-epoay t,

* a twh t r preferably not more than 7 carbon atoms. Examples the likefjPa'rticularly preferredare theepoxy-substr H t V b le k aali sq taimnsa riotmbre'thanTZ carbonatoms'i' f f If and vic-epoxy-subsntuted" alcohols wherein *the epoxy group is in a positionotherthan on a cycloaliphaticring,

. and preterably in a terminal position, such as represent a veryspecial group of compounds in that they have epoxy groups of dute rent" act vity toward epoxy curmg e eat 1' aliphatic ring ;has been -found to be less reactive withactive epoxy-"curingagents, suchas amines, than the terminal, epoxy groups, so one may first react the new polyexpoxrdes" with an amineto'torm along chain polymer through reaction with, the termmal'epoxy group andfthen this po ymer can be cross-linked v throu'gu the fepgxy group curing agents',* such' as-acidz'anhydridesxi- I?" i The new polyepoxides of the present. invention are preferably prepared by. reacting an alcohol having an ethy nic yunsa ra d q e aau h t c i s s ha f r mammal-cy e q ydri i w reac ion lh a k i tot q m the vic epoxide andi'then-treatingtheresulting ether with a peroxid' g agentjto ii l it j e ethylenic group in e gy ga phat q i o a poxy r pto process of'preparation, ifwas surprising to find that epoxidationgf theiunsatnrated linkagein the cyclo'alieta ico p ishedl w th ut afi n l the adi a ttf che l..th the-e r 111.16 i h' n g p 5. s h {as been rather] difiicultto epoxidize, the

hy ict g oup in hq 'y lqa p ati lr ng L if the 9 mm been rather Qe'a'sfy toffepoxidizieij As note'd'above, the novelZpo iyepoxides Qf the invention m y e dead dl e 'l iqfia ll li ha g a vi rep y' up iecntaihed in a f 'yi e ha l ng ianq mq y i i jrnorielv c-epoxy groups. The sedfhereinjrefersto the group 7 i-e-J here ifthi e fmm a ta ed t ti v a bf 5 atoms; Thenota'tio'nthat the vie-epoxy group iscon tained i -asycloa i h t .rin ind cates h t c bqaatoms off the: ring itself. The alcoholsj posor 7;" carbon' atoms, and may have the alcohol 6H 'gro up dfdirectly; to the ring or through an-alkylene groilp of of] these alcohols iinclude, among "others, 2,3-epoxye fiPY Arepo y c xan 2 99 2, SE PQ YW OP an L. I2-

cycloallganols'and the epoxycy us,-;thefepoxy "group on thefcjyel o- 111 an e b y hande ik a 1 -eppxy -substituted cycloaliphatic ring 's'may I I 'P Y Yd EiQm Y possess Mi -0 5.5.6

tench 2t3-ep d deea e enl-t el ihe Preter ed e x -sub t tuted aleehqle r t e o yshhst t t e l 'hetie esle e iinhatie i eh drie lei 1 9 s eentaiahis item 3 1 ee e ie as p yp i e l ZQ-eehzy e lehezseheh eeehye e eheiylmethanol, 3,4-'epoxybut'ano'l, 3,4 epoxydddecanol, '2- methyl-2,3-epoxypropanol, 3-butyl-2,3-epoxycyclohexanol, 2,3-epoxypropoxyethanol, 2,3-epoxypropoxyoctanol, and hel ke- Pa ticu arl PIQ F FQQ e ex -subs ith ed aleeh l a e th pexy ka e s epex alk x h ne s, epeay ye llsane s pe eye lalk hel epe eyele lke eXylh nq ts Vepexya kex er leallsans s ari ePer e s-twahyh llsexyalken s nd part eh erl hese eehta h h n m re han ,ee he stem .r

C mi und r sp e l eehsideratien ar the ie-e xysubs tute elee s whe in th epoxy IQ JP is ne tainee in e el al phati he but i n a e tsi ht'e h por io el theme e u een p ef r bly n a erm n l p ti s as the eehels qt theiermh e 0 cQ-on-R-ou wherein Ris a bivalent aliphatic hydrocarbon radical. As noted above, ether-s prepared from these special epoxy alcohols present epoxy groups that have different activity toward curing agnts'and the epoxy group in the cycloali phatictring. These special properties enable them to be used to form higher molecular'weight products before cross-linking as indicated hereinafter I Examples of the novel .ethers vof the present invention include, among others 2, 3.-epoxypropyl 2,3-.epo'xycyclo hexyl ether, 3,4.-epoxybuty1 2,3-epoxycyclohexyl ether, 2,- -epe yp' epyl 2, 4 p x eye my e h 2J -eP n ep 3 -ep yi y e j p l e e 2 3-epexy"p py p y e y lt e h et .3 einex n py (2J3- eperg eye ehe yhp opyl et 3,4 p y'd d vl 1 1 epoxycyclohexyl" ether, the 'diether of 2,3- epoxycycloh ex- @5 0 read et le y l the d th 0 2 3-. pe Y Y piem and 'h t ehe s yeel, thediethe 2 hy epoxycyclohexanolan'd l,5-pentanedi ol, the diether of 2,3- epoxycyclopentanol and sulfonyldipropanol, the triether of 2,3-epoxycyclohexanol and glycerol, di(2,3-epoxycyclohexyl) ether, 2,3-epoxypropoxypropy12,3-epoxycyclohexyl ether, 2,3-epoxypropyl 2,3,5,6-diepoxycyclohexyl ether and 2,3-epoxypropyl 2,3-epoxy-5-chlorocyclohexyl' ether and the like, V

Preferred polyepoxides of the present invention include the epoxyalkyl, epoxycycloalkyl epoxyalkoxyalkyl and epoxycycloalkoxyalkyl'ethers of epoxycyc loalkanols or epoxycycloalkylallganols, such as, for example, 2,3-epoxyprepy ,3-ep yey 1 h 1 et er; g (3,4=ene y yl) ether, 2,3-epoxypropoxybutyl 2,3-epoxycyclohexyl ether, 2 -epqze p epy (2, exy e e y y ethe 3- epe y eh xy y net 2 3 pexy y le xy t AS et dabe e the P t e fly Pref r e ne yepexi e pe t .a y besehs Q th r ar able ei tir tr tewejrd entriagepts are those ethers of the epoxy yqbalkanols and epes e eleelk l l eneh wh rein th ethe exy a e are n th terminal P eit en? u h a. fe example; 23- epezynrepy 2a e b yeye oh x ether,1 ,4.-epe vhutr 2,3-epoxycyclohexyl ether, 2, 2 epoxyprbpyl (2,3-epoxycycl0hexyl)butyl ether and 2,3-epoxydodecyl 2,3-epoxycyclopentyl ether.

The novel compounds of the invention may be prepared by a variety of methods. They may be prepared, for example, by epoxidiz ing the eorresponding polyethylenically unsaturated ether,"i'.e., anether of an alcohol having an ethylenically unsaturated cycloaliphatic ring and a monohydric alcohol possessing an ethylenic group. 2,3- epoxypropyl 2,3-epoxycyclo-hexyl ether may be prepared by this method, for example, by epoxidiging allyl 2-cyclohexenyl ether. The polyethylenically unsaturated ethers may be prepared by conventional methods from the unsaturated alcohols. Thus, allyl 2-cycl0hexenyl ether may be prepared by reacting allyl chloride with 2-cyclohexenol in the presence of NaOH. 'Di(2-cyclohexenyl) ether of ethylene glycol may be prepared by this method, for example, by reacting 2 moles of 2-cyclohexenyl alcohol with 1 moletof cthylenedichloride in the presence of 2 moles 'N' QI-I- Th ype eI eth ifiee s eaetieh s Pr fe b ee lue ek at i 'e er th ren h 'hem b i 5, C. to C. Solvents are not generally used if excess of the proper reagent is used but may be employed if desired or necessary.

Polyepoxides of the present invention wherein the epoxy group in the vic-epoxy-substituted monohydric alcohol is in the 2,3-position are preferably prepared by first reacting the ethylenically unsaturated cycloaliphatic alcohol with a halo-epoxy-substitjuted compound or a dihalo-hydroxy-substituted co mpoundin the presence of a condensation catalyst to form a ehlorohydr'in ether, dehydrochlorinating that product to form the epoxy ether and then epoxidizing thetether to convert the ethylenic group, in the cycloaliphatic ring to an epoxy group. 2,3-

epoxypropyl 2,3-epoxyzyclohexyl ether maybe preparedby this'method, for example,by reacting Z-cyclohexenol with epichlorohydrin to form the chlorohydrin ether of 2-cyclohexenol, dehydrochlorinating that product to form the glycidyl ether and, then treating the resulting product with a peracid to effect the epoxidation of the ethylenic group in the cyclohexenyl ring.

' The expression halo epoxysubstituted compound as used herein refers to those compounds having a 1 ,2 -epoxy group, i.e.,t a

compound as used herein refers to those compounds havjug a series of three carbonatoms one attached tdahalogeh atom,-the next is atta to a hydroxyl group-andthe lastis attached toahalogen atom, as, o ex mpl i lereirhyel eaypr pehe 2, e 3hydroxypentane, 2,3:dichlofo-B hydroxybutane, and the like. Ep i'chlorohydrin Comes under special consideration because of'its low cost and because of the superior properties of the epoxides obtained therefrom.

The halo-epoxy-substituted compound or the dihalohydroxy-sub'stituted compound and the unsaturated cycloaliphatioalcohols are preferably reacted .in chemical equiyalentratios varying from about 1 :l to 1.5:1.- As used herein, chemical equivalent amount as used in references to these reactants refers to the amount of the reactants needed to furnish one mole of thehaloepoxy-substituted compound or dihalo-hydroxy-subs tituted compound for every QH group of the alcohol molei1 -t9fbe reseted- T e reeeitieh'heW h t e hset etee eveleeliphetie alcohol and the epoxy-torming material is effected in the pre en of .e e d n htieh feete eh iie e catalyst including HF, lfI O H PO salts such as SnCl and 11 e he .eem lere The se ee r O the Cate; yei l van/" endin u on th ihrl idhe 'e s ing from about .1% to about by weight of the reactants. "The catalysts, suchas Bl' complexes, are"pref erably employed in amounts varying from about .1% 'to about 1% while the catalysts, ,such' as SnClgare prefer? ably used in amounts varying-from about:.5% to about 4%, as indicated in US. 2,260,753 and-U.S.'2,380,1 5.

The condensation may: be effected in the, presence or absence of solvents or .diluentsg In' no'stcases, itis pre ferred to employ a solvent, such as cyclohexane, benzene,l

h l l l Temperatures generally range'from about C. to 150 Q, and more preferably between Q. and C. In'general, the higher. temperatures give darkerlproda ucts and are less preferred than the lower temperatures; The condensation may becarried out in a varietyof ways. The two reactants may be mixed at room temperature andlthe catalyst then added, or thecatalyst may be added to one reactant and the other reactant added 'to' p that mixture. V

The chlorohydrin product obtained by the above' reaction is then treated with an alkalinematerial to dehydrohalogenate the product. This treatment may be accomplished by adding the alkalinematerial'to the reaction mixture obtained in the above described process,

or the condensation product may be recovered from the" reaction mixture by any suitable means, such asdistillation, extraction, and the like,'before it is combined with the alkaline material. "Any of the'known dehydrohalo'-' genating materials may be used in this'reaction, such as matelfonenioleof the epcxidizfing'agentf iln-somecases, it "is rather difiicult to efiect epoxidation of all of the ethylenie-groups and if acompletely epoxidized product a is required, additionalhepoxidizin g agent and/or longer I reaction'p eriodsmaybe required. Y Y I It is preferred to carry outftheep oxidation reaction in a suitable, mutual solventf or the reactants and product.-

chlor'oforin is anespecially useful solventfor the purpose,-

but other materials, such as ethyl retlier', dichlorornethane, benzene, ethyl acetate, etc., and the like maybe used. It

" is not necessaryvto operate under anhydrous conditions,

sodium and potassium hydroxide, fsodiumand potassiumj carbonates-and bicarbonatesj, hydroxidesor magnesium; zinc, lead; ,iron and aluminum, and the. corresponding}. oxides; etc. The aluminates, silicates} and z'inc'ates or condensation product of epichlorohydrin and cycloshould be reactedwith approximately lmole ofthe a1 linemateriaL 'gfi 'l i In most casesgthe dehydrochlorinatingi agentf'may 'be. aPPl edto the'halohydrin as" an aqueoussolution or suspensions or dissolved-in an inert solvent, such as"ethers,'f

esters, hydrocarbons, and the like. 'Ifthefabove-note'd aluminates;i-silicates or 'zincates are usedas' the alkaline materialythe' dehydrohalogenation is preferably effected. 60. or dissolved in organic'solvents' or diluerlts; 1",4-dioxane; is. particularly satisfactory as a solvent "for this purpose in a non-aqueous medium and' the salts as'by' themselves but'the amount of water present should be limited so as to avoid excessive hydrolysis of the epoxy group or groups.

Up to 25% water in {the reaction mixture may be.

tolerated. v

The temperature employedduring the epoxidation may vary over a considerable range depending'up'onthe-type of reactants and oxidizing agent selected. It is-generally "desirable 'to maintain the temperatureb'etween -10 C.

to 60 Gland more preferably between 10 C.'and 40" C. Atmospheric, superatmospheric or subatmospheric pressures maybe employed as. desired.

' The epoxidized products obt ned by this method may be recovered from the reaction mixture by any convenient means known to the art, such as distillation, extraction,

fractionalprecipitation, filtration, and the like. v 7) 'The polyepoxides of the presentmventlon are waterwhite'toslightly yellow colored liquids to solids. They have at least two epoxy groups-permoleculeandarefsub} 30' stantia lly free of chlorine. As noted, the liquids'have low,

viscositie's and are generallysoluble in most'solvents, such as ketones,:,alcohols and-liquid hydrocarbons, and are compatible with many synthetic oils and resins.

iFo'r'certain' applications, suchas in the preparation of Y polymeric pr'oducts','it is sometimes desirable to have high molecular weight products. Such products maybe obtained byfreactin'g'the above-described new 'polyepoxides withpolyhydric compounds. In this case, the polyhydric compound'reacts with the vie-epoxy groups to form on -e-o-o groups." Highmolecularweightproducts may obtained 7 from glycidyl epoxycyclohexyl etherffor example, by re- The epoxidation. of the -'polyethylenic' a1ly unsaturated ether or theepoxy ether of the unsaturated cycloaliphatic alcoholmay be advantageously carried out by reacting the ethers with. an epoxidizing agent. :Organic per'acids,

such as 'perace tic acid, perbenzoic'acid, monoperphthalic acid'andthenlike, are preferred agentsfor this-reaction."

l .The. amount 'of" the epoxidizing agent employed will vary over a considerable range depending upon the type of 1 product? jdesired.'=i'z In general, one should' 'employ. 'at least fone; mole'of, the oxidizing agent, i such as described above, forlevery ethylenic'group to be epoxidized. Thus,

p I hydric phenol hav'in'g X OH groups.

theformulaf a r is to beconverted to an epoxy group, the above product p acting Xmoles of that compound with one. mole of; apolya 'vi hereinc R is the residue of thepolyhydric phenol and n is anlinteger representing the number of OH groups on Ithepolyhydric phenol molecule; Polyhydric compounds used forthis purpose may be any polyhydric phenol, suchasresorcinol, 2,2'-bis(4-hydroxyphenyl)propane, catechol, hydroquinon'e, methyl resorcinol," 2,2-bis(4-hydroxy-p phenyl')butane-and the-like. 7

The-condensation reaction described above for the preparation of the 'highermolecular weight products may 'be accomplished by merely heating the components to getherin the presence or absence of inert diluents. The I condensation reaction is preferably accomplished at ternQ peratures'ranging from about25 C. to 200C. and more 'preferablyrfrom'1505C. to about 200C. T lfithe' resulting hi'ghmolecular weightproductspos sess lessi'tha'n .the. desired number of e b 'y: 'g qij QliShhlfi' may be the we when t P Y 1Y P bli1isreacted amiss than m n y memew'pblre Such products have n xi e ddi nal-even eas ma e i ed by reacting the higher molecular weight products with addienel q a e f. the ear-teem n at r a th epoxy-halo-alkanes, such that there will be one epoxy group for each of the OH groups of the polyhydric phenol to be reacted. Thus, if the higher molecular weight product was obtained by reacting one mole of glycidylepoxycyclohexyl ether with two moles oi the dihydric phenol, the resulting higher molecular weightproduct would then b reacted. h a p x matel tw melee ef th ay forming material. The halohydrin obtgined may then be dehydrohalogenated according to conventional procedure. The higher molecular weight products produced by the above methods vary fron't viscous to solids having relatively high melting points. They possess active epoxy groups as well as hydroxyl groups and may be cured or uud ef r e aetien th e a ei her at the e aaet ene o ps. a

The n p ye x d e the n entieeaa h irhishet m e e e ht me uete a? 9i 1 E m y be eured t u the P XY een t term elt eble rel meric products. They may be polymerized alonec uwith other polyepoxide materials in a variety of different proportions, such as, for example, with amounts of other polyepoxides varying from 1% to 95% by weight. Polyepoxides that may be copolymerized with these products of the present invention include, arnong othersgglycidyl polyethers polyhydric phenols obtained by reacting polyhydric phenols, such as bis-phenohA, resorcinol, and.

the like, with an excess of chlorohydrin, such as epichloro hydrin, polyepoxide polyethers obtained by reacting an a lkane polyol, such as glycerol andsorbitol, withepichlorohydrin and dehydrohalogenating the resulting product, polymers p repared from ethylenically unsaturated epoxidesfsuch a'e allyl glycidyl ether, alone or with other ethylenically unsaturated imonorners, and polyepoxide polyethers obtained by reacting a polyhydric alcohol or polyhydric phenol with any of the above-described polyepoxides. The glycidyl poiyethers of polyhydric phenols obtained by condensin'g the polyhydric phenols with epichlorohydrin as described above are often referred to as ethoxyline resins. See Chemical Week, vol. 69, page 27, for September 8, 195 1.

A more detailed description of these polyepoxides and etc; phosphoricacid and partial esters thereof including n-butyl ortho-phosphate, diethyl ortho-phosphate, hexaethyl tetraphosphate; amine compounds, such as triethylamine, ethylene diamine, diethylamine, diethylene triamine, triethylene tetraamine, dicyandiamide, melamine; and salts of inorganic acids, such as zinc fluoborate, potassiurn persulfate, nickel fiuoborate and magnesium perchlorate. V

The amount of the curing agents employed may. vary over a considerable range depending upon the agent se lected. .With curing agents having replaceable hydrogen, such as the amine curing agents, amounts of agent em.- ployed vary up to and including equivalent proportions, i.e., sufficient curing agent to furnish a replaceable hydrogen atom for every epoxy group to be reacted. In most cases, satisfactory cures are. obtained with from .-7 to 1 equivalent of the curing agent per equivalent of epoxy compound.

Other curing egents, such as metal salts, are employed in amounts varying. from about 1% to about 20%, and more preferably from about 3%. to.20%.

The cure of the polycppxides is preferably .eifected .by

mi h cur ae a e i th pe p x an h n heating. The temperature selected will vary with the curingagent. Active curing agents, suchv as the amines may be utilized, forexa 'ple, atlower temperatures, such as from room-temperat Te toabout 60 C. Less active materials, such as polyasic anhydrides and acids, generally require higher temperatures, such as temperatures ranging frornabout 60 C. to C. Aromatic amines are preferably employed at the higher temperatures, e.g., temperaturesranging fromabout 60 C. to 150 C.

if the new polyepoxides or their higher molecular weight derivatives are to be used in the preparation of castingsorpottings, the curing agent and the epoxy mae iel ar ne al y eet ait d e e e d hen e e m th meld e eetia Whi h m ,if e red er ain ed ea ae rie v eueh. a e etIieeI WW5: a aratu t an he Hue then h ated t9 efiee he sur h jn w gel e eze e ear the r hi h el r We h de iva i ee ma a o be egmle ee w th h e eredescribed curing agents to prep-are improved surtace coat: ing compositions of the air-drying or baking type. In utilizing the products for this application, it is generally desirable to combine the epoxy material and the curing agent with the desired solvents, and, if desired, other filmforrning materials and driers, and then apply the resulting mixture to the surface to be coated. .Film-forrning materials that can be used with the epoxy material in .this manner include the drying oils, such as tung oil, linseed oil, dehydrated castor oil, soyabean oil, and the like; cellulose derivatives such as cellulose nitrate, cellulose acetate,

cellulose acetate butyrate, cellulose propionate, ethyl cellulose, and the mixtures thereof; and vinyl polymers, such as polymers of vinyl chloride, vinylidene chloride, methyl methacrylate, diallyl phthalate, and the like. ,i'IEhecoatings prepared in this manner may be allowed to set to a hard finish at room temperature or heatmay the applied to hasten the cure. e

The higher molecular weight hydroxy-containing derivatives of the new polyepoxides as described above are particularly suited for use inpreparing coating compositions as described above, as they may be reacted through the hydroxyl group or groups with dryingoil fatty acids or may be ,cured through the hydroxyl groups'with compounds, such as methylol ureas, methylol phenols, .diiso-. cyanates, and the like.

The new polyepoxides and their higher molecular weight derivatives may also be employed with the curing agents to prepare valuable adhesive and impregnating compositions. In utilizing the products for these applications, itis generally desirable to combine the epoxy mar al wi su t b sol en o dilu nts, such a benzen toluene, acetonitrile, andthe like, so as-to form a spread-;

able fluid and then the curing agent added and themixture applied to the desired surface. e

In addition t'o their use in forming theiabovedescribed.

polymeric products, the new polyepoxides and their higher molecular weight derivatives may be used as stabilizing agents for varioushalogen-containing polymers; and par-' ticularly the vinyl halide polymers. These products "are compatible with the polymers-andgin combination therewith give good resistance to discoloration by heat and light. These productsmay be used as stabilizers, alone or in combination with other stabilizing agents, suchas urea and thiourea derivatives. In most cases, the products are effective as stabilizers in amounts varying from about .1% to 5% by weight of the polymer being stabilized. The epoxy material may be combined with the halogencontaining polymer ,by any suitable method, .such as by dissolving the products in a suitable solvent or by milling the products'together a suitable roll mill.

To illustrate the-manner in which the invention may be carried out, the following examples are given. his who understood that the examples are for the purposeof illustration and the invention .is not to be regarded 'as limited to. pf the-specific com ounds ,or conditions recited parts of chloroform. The mixture was; cooledto C. m am he curedwith meta-phenylene idifroni epichldroliydrin arid cyclohex'enol addedto-200 ne --5 a na 2 3; p p z,g epoxycyclohexyl sipar' s dfa'q'm perace i'c acidsoliitidn addedthere 1 V Y to; "After;holdingat s C." for 1li6ur, tigetemperature, t mple lll v,

wasraised'to' about'20" cs and held there risr t's hoius This example e tth Prep some of The reaction mixture was then 'extracted' "water, i th P fi ;3,'PQXYR 9PY ,(lti-ep x c o x l) sodium carbonate; water 'a ud 'thenffilteredand dried. methyl hi a j "Y v H f 'j v Chloroforrn'was thentak en ofi'and'theproduct distilled Parts? of x i3- x p op y y to yield a white free flowinglidriid havifi g" 0.0 poise, ether p p -by r a ti :tetr h b n y a hol with a aiaxyeyciapeat i are hayn /131147 and epoxy lu f 1 /10() g! The parts of a pera'cet ic 'acid solution was then added product wa v23 ",'poxypmpyl v2,3 epo'xyt(Emlohkmd ethcr to the'mi'xture-and the "resulting mixture maintained at;

s ia t t e 730 for 2 hou'rs'a1id the allowedto stand in ar water,

f bath at 27 'fonlZhQurSQ 'The reaction mixture was 1 t I -i l I 1 thenei'ttracted with" water, sodium carhonatd water and v a i 1 1 ,thenfiltered and ldried Chloroformfwas then taken ofi 0 ----(-3H 25 and thiproduct' distilled to yield a water white free flow propyl (2,3-epoxycycloheit'yl methyl ether.

355121 1: r a j i A 1 .v with9parts of diethyle netriamine'andithe mixture main- .2 1 .-11 he pol e x rd epar ab vewas a o wanted gues -0.1 sewn-linens. The resulting prod-g mixed with 32 parts-of'meta-phenylene diarnine and-:the; t'Iw f nhi-dish ti gih inb at r as m r 19 19 9 bta ned t omcasting gg niix'tur'-"heat'eduo" 150- f qdis i n t water,

phcn pp i h-12 %metarph n aedi m ne o haranes s vame. 'The'Tprbduct-was also- 'i'esis t'antgto' water;

100 parts of 2,3-epoiiyprhpyl (2,3-epoxycyclohexyl) fl rgllyep qxide a 25m; ;s0-. o.-12o=o. 14s c. 165C. the mixture maintained at- 100 C for several hours. The resulting 'pr oduct wa's a hard ca "the ' Theproduct wasalso resistant-to waten-allt aliand solyentsf ii 'h fi y tained at 100 C. for several;hours:v 'The-resulting'prod P 1? bit not .was' aithard: casting hayiflg good lresistanceto vwater,

parts triphenyl-phosphine. The mixture was kept at 100 C. for $6 hgur and the mixture then gelled. After 1 in inuate l i st 7 ether.

I pared from epichlorohydrin and cyclopentenolwas added methyl .ether tni) d;,With 9 0;p"arts ofjhexahydro phthalic ahliydride and 1;.p art ofibenzyldimethylamine audf sting having good resist-j properties. of the di( 2g3-epoxycyclohexyl) ether of and .-1 part of ben'zyldimethylamineiand thetmixturemain- 1 ig'vlyiczol i'z1oo siartszof the polyepoitideiwasmiked ammo V s w dit g fidg y aw er} at l' -C- for 12 hours.

hexahydrophthalic anhydride, warmed and stirred iir z Iltl aq "r wasjihenfiaken' 0a and the product. distilled ater h" 'quidfidetified as di( 2,3-epoxy- 2 hoursapaleyellow; obtained.

'hthalicfanhydride, dichloromaleic aupreparation and somelz oi 7' V he zpmp o .2,3-.ep oxyp p 100' parts of 2,3-epoxypropyl 2-cyclopentyletherpre- Example to 400 parts of chloroform. 7150 parts of 45% per- J'Ihis example illustrates the preparation and some of in; the lpresence oiflcaustic,was added to 150.,

H 'roform' ,50 parts of a 45% peracetic acid solution wastheriaddd tothe miittur'eand the resulting t alkali and solvents. a v 5 mixture maintained.atQ3 0t ,for. 2 hours andith'enal- I epdiiide ouldl be care-a a with? heziahydrofl,

nhydrideflin the-preseuce of 1% 1 V ie g hsm mi acetic acid solution was then added to the mixture and the properties of 2,3-epoxypropoxyethyl 2,3-epoxycyclothe resulting mixture maintained at 30 C. 'for'2 hours 'he'xyl ether. 7 i

and then allowed to stand in a water bath at 27 ,C; for, 70 ,parts of 2,3-epoxypropoxyethyl' 2-cyclohexenyl 12 hours. The reaction mixture was then extracted with a ether (obtained by reacting 1 mole of 2-cyclohexenyl water, sodium carbonate, water and then filtered and chloride with .1 "mole of ethylene glycol and then re-' dried. Chloroform was then taken 05 and the product acting that product with epichlorohydrin) was added to distilled to yield a water white free flowing liquid iden- 300 parts of chloroform. 200 parts of a 45 j% perace'tic 11 a lh h as henadtledte the-m xture a th re sulting mixturemaintained at 30 C. for 2 hours and then allowed to stand in a water bath at 27C. for 12 hours. The reaction mixture was then extracted with water, sodium carbonate, water and then filtered and dried. Chloroform was then taken E and the product st led to y lda Water. hi e tee flowin liq d i en h s p od t wuld be cu ed w ethylene r am ne meta-phenylene diarnine and hexahydrophthalic anhydride in the same manner as shown for 2,3-epoxypropyl 2,3-epoxycyclohexyl ether in Example I;

Example VI for 12 hours. The reaction mixture was then extracted with water, sodium carbonate, water-and then filtered r e h Qr f0 m wa then a n o t n t product distilled to yield a water white liquid identified as di(2,3-epoxycyclohexyl) ether.

.0 parts o the el p xi re a e a o w i e w 1 p r he ahyd oph h lie an ydri an 1 part of benzyldimethylarnine and the mixture maintained at 100 C. for several hours. The resulting product was a hard casting having good resistance to, water, alkali and solvents.

B a d eu ed n qdh s e e Q ain d by eplaci he ex h p h i anh e (w equi alen amount Q e h of e fQ11 18iPh h 1 nhy ride. d h ereue h an drid ch er die anh dri Md. pyr me litic anhydride.

E p e Vll Two moles of 2,3-epoxypropyl 2,3-epoxycyclohexyl ether produced in Example I was combined with '1 mole of 2,2-bis(4-hydroxyphenyl)propane'"and the mixture heated at 150 C. for several hours. The resultingproduct was a soft solid which could be subsequently cured with amines to form a hard solid casting.

I claim as my invention: 7 l

p mxfle' Whieh is ame h r f (1;) an alcoh selected fromthegroup consisting of monocyclic monoh dr e pq u st tu h e el l a s d eye y w alkehels nt n n i e n 5 t 7 ca b ns n the rin wherein the oxirane oxygen is substituted on the nucleus and (2) a vic-epoxy-substituted monohydricalkanol of at e o s w e ein the e t em y n is t m na ly situated. i A po y p e hi h is an eth O a nocyclic monohydric vic-epoxy-substituted cycloallganol having from 5 to 7 carbon atoms in the ring and (2) a vicepoxy-substituted monohydric alkanol of at least 3 carbons wherein the oxirane oxygen .is terminally positioned.

'3. A polyepoxide which is anether of (l) a Vic-epoxysubstituted cyclohexanol and (2) a vic-epoxy-snbstituted monohydric alkanol having from 3 to 12 carbon atoms wherein the oxirane oxygen terminally situated.

A p poxid hie is an et r f. lm o y emonohydric vic-epoxy-substituted "cycloalkyla'lkanol have 12 ns r m 5 th 7 ear ns i the ng and wh in th epoxy'oxygen is directly attached .tothe ring and (-2,) a monohydric vic-epoxy-substituted alkanol having from 3 to 12 carbons wherein-the epoxy-oxygen atom is terminally situated. a

5. A monocyclic vic-epoxycycloalkyl ether of a-monohydric vic-epoxyalkanol of 3 to 12 carbon atoms, wherein the vic-epoxycycloalkyl group contains from 5 to 7 carbons and the epoxy-oxygen in said vic-epoxyalkanol is terminally positioned. Y

6. A monocyclic vic-epoxycylohexyl ether of a vicepoxy-substituted monohydric alkanol of '3 to 12 carbons wherein the epoxy-oxygen of said alkanol is terrnie nally situated.

-7- A ,3-ep xyp py ether of a monocyc ic mono? hyd e p xy-s s ed eyelcalkan l av n item 5 to 7 carbons in .the ring.

8- i p xyp py t er o 2 p xy ycl he ano ,9. 2,3-epoxypropyl ether of 2.3-epoxycyclopentanol,

1 Z 'PQ YP QPYI eth 0t 2 -epoxyeyc eh ylmeth anol.

11. The polymer of the polyepoxide defined in claim 1 and from 1 to 95% by weight of a polyhydric phenol.

12. The polymer of the polyepoxide defined in claim 3 and from 1 to 9.5% by weight of a polyhydric phenol.

13. The polymer obtained by reacting the polyepoxide defined in claim 3 with an amine cross-linking agent at a temperature of from about 20 C. to about 250 C., said cross-linking agent being present in a sufficient amount-to provide a replaceable hydrogen atom for sub stanti-ally every epoxy group reacted.

- 14. The polymer obtained by reacting the polyepoxide defined in claim 4 with an acid anhydride in admixture with a tertiary-amine catalyst at a temperature of from about 20 C. to about 250 C., said acid anhydride being present ina sufficient amount to provide a replaceable hydrogen atom for substantially every epoxy group reacted. 7

15. The copolymer of 2,3-epoxypropyl ether of 2,3- epoxycyclohexanol and from 1 to 95% by weight of a polyhydric phenol.

- 16. The proces for producing a monocyclic vie-epoxycycloalkyl ether of a monohydric vie-epoxy alkanol wherein the vic-epoxycycloalkyl group contains from 5 to claim 1. r

7 carbons and the epoxy-oxygen in said vie-epoxy alkanol is terminally positioned, which comprises reacting a monocyclic alkenyl ether of a vie-epoxy alkanol in which the epoxy-oxygen is terminally positioned and wherein the alkenyl ring contains from 5 to 7 carbons, "with a peracid in admixture with an inert organic solvent at a temperature of frornabout ...10 C. to about C., at least .one mole of .said peracid being present for eve ethylenic group to be epoxidized.

1.7. The homopolymer of the polyepoxide defined in 18. The homopolymer of the polyepoxide defined in claim 2.

References Cited the file of this patent UNITED STATES PATENTS 2,543,416

Niederhauser Feb. 27, 1951 2,553,718 Neway et a1. May- 22, 1951 2,642,412 Newey et a1; June 16, 1953' 2,739,161 :1956

Carlson Mar. 21), 

1. A POLYEPOXIDE WHICH IS AN ETHER OF (1) AN ALCOHOL SELECTED FROM THE GROUP CONSISTING OF MONOCYCLIC MONOHYDRIC VIC-EPOXY-SUBSTITUTED CYCLOALKANOLS AND CYCLOALKYLALKANOLS CONTAINING FROM 5 TO 7 CARBONS IN THE RING WHEREIN THE OXIRANE OXYGEN IS SUBSTITUTED ON THE NUCLEUS AND (2) A VIC-EPOXY-SUBSTITUTED MONOHYDRIC ALKANOL OF AT LEAST 3 CARBON WHEREIN THE OXIRANE OXYGEN IS TERMINALLY SITUATED. 